DISPERSION COMPOSITION

Abstract

An alcohol-based composition may contain an acryl-modified polyolefin resin and exhibit a good adhesion even at a high solid content, suppress an increase in viscosity, and have good stability such as dispersibility and sustainable stability. A dispersion composition may contain at least a modified polyolefin resin dispersed in a dispersing medium containing an alcohol solvent and an aliphatic hydrocarbon solvent. The modified polyolefin resin may be modified with a (meth)acrylic acid component containing at least a (meth)acrylic ester of formula (I) and a (meth)acrylic ester of formula (II). The total content of the structure derived from the (meth)acrylic acid component in the dispersion composition is 3% to 94% by weight, relative to 100% by weight as a total amount of the modified polyolefin resin and (meth)acrylic acid component polymer, and a solid fraction in the dispersion composition is 30% to 80% by weight.

Claims

1. A dispersion composition, comprising: (A) a modified polyolefin resin; and (B) a dispersing medium comprising an alcohol solvent and an aliphatic hydrocarbon solvent, wherein the modified polyolefin resin (A) is dispersed in the dispersing medium (B), wherein the modified polyolefin resin (A) is modified by a (meth)acrylic acid component comprising (C) a (meth)acrylate ester of formula (I):
CH.sub.2═C(R.sup.1)COOR.sup.2  (I), R.sup.1 being H or a methyl group; and R.sup.2 being —C.sub.mH.sub.2mOH, with m being an integer in a range of from 1 to 18; and (D) a (meth)acrylic ester of formula (II):
CH.sub.2═C(R.sup.3)COOR.sup.4  (II), R.sup.3 being H or a methyl group; and R.sup.4 being a linear, a branched, and/or a cyclic alkyl group having 4 to 18 carbon atoms, wherein a total content of a structure derived from the (meth)acrylic acid component in the dispersion composition is in a range of from 3 to 94 wt. %, relative to 100 wt. % as a total amount of the modified polyolefin resin (A) and (meth)acrylic acid component polymer, and wherein a solid fraction in the dispersion composition is in a range of from 30 to 80 wt. %.

2. The dispersion composition of claim 1, wherein the content of a structure derived from the (meth)acrylate ester (C) in the modified polyolefin resin (A) is 20 mol. % or less, relative to 100 mol. % as a total content of the structure derived from the (meth)acrylic acid component.

3. The dispersion composition of claim 1, wherein the content of a structure derived from the (meth)acrylic ester (D) in the modified polyolefin resin (A) is 25 mol. % or more, relative to 100 mol. % as the total content of the structure derived from the (meth)acrylic acid component.

4. The dispersion composition of claim 1, wherein a weight-average molecular weight of the modified polyolefin resin (A) is in a range of from 5,000 to 400,000.

5. The dispersion composition of claim 1, wherein the modified polyolefin resin (A) is further modified with an acid component other than the (meth)acrylic acid component.

6. The dispersion composition of claim 1, wherein the modified polyolefin resin (A) is further chlorinated.

7. The dispersion composition of claim 6, wherein a degree of chlorination of the modified polyolefin resin (A) is 30 wt. % or less, relative to 100 wt. % as a weight of the modified polyolefin resin (A) excluding a weight derived from the (meth)acrylic acid component.

8. A primer, comprising: the dispersion composition of claim 1.

9. An adhesive, comprising: the dispersion composition of claim 1.

10. A binder suitable for a paint, the binder comprising: the dispersion composition of claim 1.

11. A binder suitable for an ink, the binder comprising: the dispersion composition of claim 1.

Description

EXAMPLES

[0175] Hereinafter, the present invention will be specifically described by using Examples, but the present invention is not limited to these Examples. Note that the unit “parts” used below means “parts by mass”. The temperature condition in the following description is a room temperature (25° C.) unless otherwise specifically mentioned. The pressure condition is under a normal pressure (1 atm) unless otherwise specifically mentioned.

Production Example 1: Acid-Modified Chlorinated Polyolefin Resin (A-1)

[0176] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight and the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L/D=60, diameter=15 mm, the first barrel to the fourteenth barrels).

[0177] The reaction was carried out with the residence time of 10 min, the rotation speed of 200 rpm, and the barrel temperature of 100° C. (the first and second barrels), 200° C. (the third to eighth barrels), 90° C. (the ninth and tenth barrels), and 110° C. (the eleventh to fourteenth barrels). Then, the unreacted maleic anhydride was removed under reduced pressure to obtain an acid-modified polyolefin resin modified with maleic anhydride.

[0178] One hundred parts of the acid-modified polyolefin resin was fed into a glass-lined reaction vessel. Chloroform was added, and the resin was thoroughly dissolved at the temperature of 110° C. and the pressure of 2 kgf/m.sup.2; then, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added. The chlorination was carried out by blowing a chlorine gas while controlling the pressure inside the vessel at 2 kgf/cm.sup.2.

[0179] After the reaction, 6 parts of an epoxy compound (Epocizer W-100EL, manufactured by DIC Corp.) was added as the stabilizer, and then, the resulting mixture was fed to a vented extruder equipped with a solvent-removing suction unit at the screw shaft portion to remove the solvent and solidify to obtain the acid-modified chlorinated polyolefin resin (A-1). The acid-modified chlorinated polyolefin resin (A-1) thus obtained had the weight-average molecular weight of 60,000, the degree of modification with maleic anhydride of 2.5% by weight, and the chlorine content of 15% by weight.

Production Example 2: Chlorinated Polyolefin Resin (A-2)

[0180] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight, the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst was fed into a glass-lined reaction vessel. Chloroform was added, and the resin was thoroughly dissolved at the temperature of 110° C. and the pressure of 2 kgf/m.sup.2; then, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added. The chlorination was carried out by blowing a chlorine gas while controlling the pressure inside the vessel at 2 kgf/cm.sup.2.

[0181] After the reaction, 6 parts of an epoxy compound (Epocizer W-100EL, manufactured by DIC Corp.) was added as the stabilizer, and then, the resulting mixture was fed to a vented extruder equipped with a solvent-removing suction unit at the screw shaft portion to remove the solvent and solidify to obtain the chlorinated polyolefin resin (A-2). The chlorinated polyolefin resin (A-2) thus obtained had the weight-average molecular weight of 60,000 and the chlorine content of 15% by weight.

Production Example 3: Acid-Modified Polyolefin Resin (A-3)

[0182] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight and the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L/D=60, diameter=15 mm, the first barrel to the fourteenth barrels).

[0183] The reaction was carried out with the residence time of 10 min, the rotation speed of 200 rpm, and the barrel temperature of 100° C. (the first and second barrels), 200° C. (the third to eighth barrels), 90° C. (the ninth and tenth barrels), and 110° C. (the eleventh to fourteenth barrels). Then, unreacted maleic anhydride was removed under reduced pressure to obtain an acid-modified polyolefin resin (A-3) modified with maleic anhydride.

[0184] The acid-modified polyolefin resin (A-3) thus obtained had the weight-average molecular weight of 60,000 and the degree of modification by maleic anhydride of 2.5% by weight.

Production Example 4: Acid-modified Chlorinated Polyolefin Resin (A-4)

[0185] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight and the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst, 4 parts of maleic anhydride (α,β unsaturated carboxylic anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L/D=60, diameter=15 mm, the first barrel to the fourteenth barrels).

[0186] The reaction was carried out with the residence time of 10 min, the rotation speed of 200 rpm, and the barrel temperature of 100° C. (the first and second barrels), 200° C. (the third to eighth barrels), 90° C. (the ninth and tenth barrels), and 110° C. (the eleventh to fourteenth barrels). Then, the unreacted maleic anhydride was removed under reduced pressure to obtain an acid-modified polyolefin resin modified with maleic anhydride.

[0187] One hundred parts of the acid-modified polyolefin resin was fed into a glass-lined reaction vessel. Chloroform was added, and the resin was thoroughly dissolved at the temperature of 110° C. and the pressure of 2 kgf/m.sup.2; then, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added. The chlorination was carried out by blowing a chlorine gas while controlling the pressure inside the vessel at 3 kgf/cm.sup.2.

[0188] After the reaction, 6 parts of an epoxy compound (Epocizer W-100EL, DIC Corporation) was added as the stabilizer, and then, the resulting mixture was fed to a vented extruder equipped with a solvent-removing suction unit at the screw shaft portion to remove the solvent and solidify to obtain the acid-modified chlorinated polyolefin resin (A-4). The acid-modified chlorinated polyolefin resin (A-4) thus obtained had the weight-average molecular weight of 60,000, the degree of modification with maleic anhydride of 2.5% by weight, and the chlorine content of 25% by weight.

Production Example 5: Acid-Modified Chlorinated Polyolefin Resin (A-5)

[0189] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight and the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L/D=60, diameter=15 mm, the first barrel to the fourteenth barrels).

[0190] The reaction was carried out with the residence time of 10 min, the rotation speed of 200 rpm, and the barrel temperature of 100° C. (the first and second barrels), 200° C. (the third to eighth barrels), 90° C. (the ninth and tenth barrels), and 110° C. (the eleventh to fourteenth barrels). Then, the unreacted maleic anhydride was removed under reduced pressure to obtain an acid-modified polypropylene resin modified with maleic anhydride.

[0191] One hundred parts of the acid-modified polypropylene resin was fed into a glass-lined reaction vessel. Chloroform was added, and the resin was thoroughly dissolved at the temperature of 110° C. and the pressure of 2 kgf/m.sup.2; then, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added. The chlorination was carried out by blowing a chlorine gas while controlling the pressure inside the vessel at 2 kgf/cm.sup.2.

[0192] After the reaction, 6 parts of an epoxy compound (Epocizer W-100EL, manufactured by DIC Corp.) was added as the stabilizer, and then, the resulting mixture was fed to a vented extruder equipped with a solvent-removing suction unit at the screw shaft portion to remove the solvent and solidify to obtain the acid-modified chlorinated polyolefin resin (A-5). The acid-modified chlorinated polyolefin resin (A-5) thus obtained had the weight-average molecular weight of 110,000, the degree of modification with maleic anhydride of 2.0% by weight, and the chlorine content of 17% by weight.

Production Example 6: Acid-Modified Chlorinated Polyolefin Resin (A-6)

[0193] One hundred parts of the polyolefin resin (propylene-based random copolymer with the propylene component unit content of 96% by weight and the ethylene component unit content of 4% by weight) produced using a metallocene catalyst as the polymerization catalyst, 4 parts of maleic anhydride (α,β-unsaturated carboxylic anhydride), and 2 parts of di-tert-butyl peroxide (radical reaction initiator) were uniformly mixed and fed into a twin-screw extruder (L/D=60, diameter=15 mm, the first barrel to the fourteenth barrels).

[0194] The reaction was carried out with the residence time of 10 min, the rotation speed of 200 rpm, and the barrel temperature of 100° C. (the first and second barrels), 200° C. (the third to eighth barrels), 90° C. (the ninth and tenth barrels), and 110° C. (the eleventh to fourteenth barrels). Then, the unreacted maleic anhydride was removed under reduced pressure to obtain an acid-modified polypropylene resin modified with maleic anhydride.

[0195] One hundred parts of the acid-modified polypropylene resin was fed into a glass-lined reaction vessel. Chloroform was added, and the resin was thoroughly dissolved at the temperature of 110° C. and the pressure of 2 kgf/m.sup.2; then, 2 parts of 2,2-azobisisobutyronitrile (radical reaction initiator) was added. The chlorination was carried out by blowing a chlorine gas while controlling the pressure inside the vessel at 2 kgf/cm.sup.2.

[0196] After the reaction, 6 parts of an epoxy compound (Epocizer W-100EL, manufactured by DIC Corp.) was added as the stabilizer, and then, the resulting mixture was fed to a vented extruder equipped with a solvent-removing suction unit at the screw shaft portion to remove the solvent and solidify to obtain the acid-modified chlorinated polyolefin resin (A-6). The acid-modified chlorinated polyolefin resin (A-6) thus obtained had the weight-average molecular weight of 60,000, the degree of modification with maleic anhydride of 2.5% by weight, and the chlorine content of 24.5% by weight.

Example 1: Production of Dispersion Composition (B-1)

[0197] One hundred parts of the acid-modified chlorinated polyolefin resin (A-1) was dissolved in 264.1 parts of methylcyclohexane (aliphatic hydrocarbon solvent); and then, 1.0 part of an epoxy compound (Epocizer W-131, manufactured by DIC Corp., 1.0% by weight to the acid-modified chlorinated polyolefin resin (A-1)) was added.

[0198] Under a nitrogen atmosphere at 85° C., 5.0 parts of Niper BMT-K40 (manufactured by Nippon Oil & Fats Co., Ltd.) (radical reaction initiator) was added with stirring (3.2% by weight to the (meth)acrylic acid component to be described below). After one hour of holding, a mixed solution ((meth)acrylic acid component) of 3.8 parts of methacrylic acid, 28.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate was continuously added over 3 hours; then, the resulting mixture was held at 85° C. for 6 hours to obtain the modified polyolefin resin with the molecular weight of 80,000.

[0199] After the reaction was completed, 100 parts of the reaction solution was concentrated under reduced pressure at 90° C. by distilling out 37.6 parts of methylcyclohexane (aliphatic hydrocarbon solvent) with stirring; and then, 57.6 parts of isopropanol (alcohol solvent) was added over about 2 hours with stirring at 70° C. to obtain the dispersion composition (B-1) of the modified polyolefin resin.

Example 2: Production of Dispersion Composition (B-2)

[0200] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 22.5 parts of 2-hydroxyethyl acrylate to obtain the dispersion composition (B-2).

Example 3: Production of Dispersion Composition (B-3)

[0201] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 33.6 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 2.0 parts of 2-hydroxyethyl acrylate to obtain the dispersion composition (B-3).

Example 4: Production of Dispersion Composition (B-4)

[0202] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 73.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 5.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate to obtain the dispersion composition (B-4).

Example 5: Production of Dispersion Composition (B-5)

[0203] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 58.1 parts of methyl methacrylate, 8.1 parts of cyclohexyl methacrylate, 36.9 parts of n-butyl methacrylate, 35.6 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate to obtain the dispersion composition (B-5).

Example 6: Production of Dispersion Composition (B-6)

[0204] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 13.1 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, 20.6 parts of 2-methoxyethyl acrylate, and 22.5 parts of 2-hydroxyethyl acrylate to obtain the dispersion composition (B-6).

Example 7: Production of Dispersion Composition (B-7)

[0205] The modification and dispersion were carried out in the same manner as in Example 1, except that the amount of the (meth)acrylic acid component fed to the acid-modified chlorinated polyolefin resin (A-1) was changed so as to give the ratio, acid-modified chlorinated polyolefin resin (A-1)/(meth)acrylic acid component=95/5 (mass ratio), to obtain the dispersion composition (B-7).

Example 8: Production of Dispersion Composition (B-8)

[0206] The modification and dispersion were carried out in the same manner as in Example 1, except that the amount of the (meth)acrylic acid component fed to the acid-modified chlorinated polyolefin resin (A-1) was changed so as to give the ratio, acid modified chlorinated polyolefin resin (A-1)/(meth)acrylic acid component=10/90 (mass ratio), to obtain the dispersion composition (B-8).

Example 9: Production of Dispersion Composition (B-9)

[0207] The modification and dispersion were carried out in the same manner as in Example 1, except that the amount of the (meth)acrylic acid component fed to the acid-modified chlorinated polyolefin resin (A-1) was changed so as to give the ratio, acid modified chlorinated polyolefin resin (A-1)/(meth)acrylic acid component=80/20 (mass ratio), to obtain the dispersion composition (B-9).

Example 10: Production of Dispersion Composition (B-10)

[0208] The modification and dispersion were carried out in the same manner as in Example 1, except that the amount of the (meth)acrylic acid component fed to the acid-modified chlorinated polyolefin resin (A-1) was changed so as to give the ratio, acid modified chlorinated polyolefin resin (A-1)/(meth)acrylic acid component=60/40 (mass ratio), to obtain the dispersion composition (B-10).

Example 11: Production of Dispersion Composition (B-11)

[0209] The modification and dispersion were carried out in the same manner as in Example 1, except that the amounts of methylcyclohexane (aliphatic hydrocarbon solvent) to be removed under reduced pressure and of isopropanol (alcohol solvent) to be added were changed, while keeping the final solvent ratio without change, so as to give the final solid content of 30% by weight relative to 100 parts of the reaction solution after completion of the reaction to obtain the dispersion composition (B-11).

Example 12: Production of Dispersion Composition (B-12)

[0210] The modification and dispersion were carried out in the same manner as in Example 1, except that the chlorinated polyolefin resin (A-2) was used in place of the acid-modified chlorinated polyolefin resin (A-1) to obtain the dispersion composition (B-12).

Example 13: Production of Dispersion Composition (B-13)

[0211] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified polyolefin resin (A-3) was used in place of the acid-modified chlorinated polyolefin resin (A-1) to obtain the dispersion composition (B-13).

Example 14: Production of Dispersion Composition (B-14)

[0212] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-4) was used in place of the acid-modified chlorinated polyolefin resin (A-1) to obtain the dispersion composition (B-14).

Example 15: Production of Dispersion Composition (B-15)

[0213] The modification and dispersion were carried out in the same manner as in Example 1, except that the addition amount of the radical reaction initiator (Niper BMT-K40 (manufactured by Nippon Oil & Fats Co., Ltd.)) was changed to 0.5% by weight relative to the amount of the (meth)acrylic acid component to obtain the dispersion composition (B-15).

Example 16: Production of Dispersion Composition (B-16)

[0214] The modification and dispersion were carried out in the same manner as in Example 1, except that the addition amount of the radical reaction initiator (Niper BMT-K40 (manufactured by Nippon Oil & Fats Co., Ltd.)) was changed to 6.4% by weight relative to the amount of the (meth)acrylic acid component to obtain the dispersion composition (B-16).

Example 17: Production of Dispersion Composition (B-17)

[0215] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-5) was used in place of the acid-modified chlorinated polyolefin resin (A-1), and that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-5) was changed to the mixture of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate, and n-butyl alcohol (alcohol solvent) was used in place of isopropanol (alcohol solvent), to obtain the dispersion composition (B-17).

Example 18: Production of Dispersion Composition (B-18)

[0216] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-6) was used in place of the acid-modified chlorinated polyolefin resin (A-1), and that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-6) was changed to the mixture of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate, and n-butyl alcohol (alcohol solvent) was used in place of isopropanol (alcohol solvent), to obtain the dispersion composition (B-18).

Example 19: Production of Dispersion Composition (B-19)

[0217] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-5) was used in place of the acid-modified chlorinated polyolefin resin (A-1), and that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-5) was changed to the mixture of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate, and neoethanol PIP (mixed solution of ethanol, isopropyl alcohol, and n-propyl alcohol) (alcohol solvent) was used in place of isopropanol (alcohol solvent), to obtain the dispersion composition (B-19).

Example 20: Production of Dispersion Composition (B-20)

[0218] The modification and dispersion were carried out in the same manner as in Example 1, except that the acid-modified chlorinated polyolefin resin (A-6) was used in place of the acid-modified chlorinated polyolefin resin (A-1), and that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-6) was changed to the mixture of 3.8 parts of methacrylic acid, 30.0 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 47.0 parts of n-butyl methacrylate, 35.7 parts of 2-methoxyethyl acrylate, and 5.6 parts of 2-hydroxyethyl acrylate, and neoethanol PIP (alcohol solvent) was used in place of isopropanol (alcohol solvent), to obtain the dispersion composition (B-20).

Comparative Example 1: Production of Dispersion Composition (B-1′)

[0219] One hundred parts of the acid-modified chlorinated polyolefin resin (A-1) was dissolved in 108 parts of methylcyclohexane (aliphatic hydrocarbon solvent), and then, 1.0 part of an epoxy compound (Epocizer W-131, manufactured by DIC Corp.) was added so as to be 1.0% by weight relative to the polyolefin resin (A).

[0220] One hundred parts of the resulting resin solution was concentrated under reduced pressure at 90° C. by distilling out 37.6 parts of methylcyclohexane (aliphatic hydrocarbon solvent) with stirring; and then, 57.6 parts of isopropanol (alcohol solvent) was added over about 2 hours with stirring at 70° C. The resin component did not disperse, so that the dispersion composition (B-1′) could not be obtained.

Comparative Example 2: Production of Dispersion Composition (B-2′)

[0221] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 35.6 parts of methyl methacrylate, 28.1 parts of cyclohexyl methacrylate, 46.9 parts of n-butyl methacrylate, and 35.6 parts of 2-methoxyethyl acrylate. The resin component did not disperse, so that the dispersion composition (B-2′) could not be obtained.

Comparative Example 3: Production of Dispersion Composition (B-3′)

[0222] The modification and dispersion were carried out in the same manner as in Example 1, except that the mixture of the (meth)acrylic acid components relative to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to the mixture of 3.8 parts of methacrylic acid, 56.2 parts of methyl methacrylate, 82.5 parts of 2-methoxyethyl acrylate, and 7.5 parts of 2-hydroxyethyl acrylate. The resin component did not disperse, so that the dispersion composition (B-3′) could not be obtained.

Comparative Example 4: Production of Dispersion Composition (B-4′)

[0223] The modification and dispersion were carried out in the same manner as in Example 1, except that the amount of the (meth)acrylic acid component fed to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed so as to give the ratio, acid modified chlorinated polyolefin resin (A-1)/(meth)acrylic acid component=5/95 (mass ratio), to obtain the dispersion composition (B-4′).

Comparative Example 5: Production of Dispersion Composition (B-5′)

[0224] The resin solution after having been modified with the (meth)acrylic acid component in the same manner as in Example 1 was solidified in an extruder; then, 150 parts of isopropanol (alcohol solvent) was added to 100 parts of the solid resin with stirring at 90° C. over 2 hours. The resin component did not disperse, so that the dispersion composition (B-5′) could not be obtained.

Comparative Example 6: Production of Dispersion Composition (B-6′)

[0225] The modification and dispersion were carried out in the same manner as in Example 1, except that the methylcyclohexane (aliphatic hydrocarbon solvent) fed to 100 parts of the acid-modified chlorinated polyolefin resin (A-1) was changed to n-butyl acetate. The resin component once dispersed deposited, so that the dispersion composition (B-6′) could not be obtained.

Comparative Example 7: Production of Dispersion Composition (B-7′)

[0226] The modification and dispersion were carried out in the same manner as in Example 1, except that the amounts of methylcyclohexane (aliphatic hydrocarbon solvent) to be removed under reduced pressure and of isopropanol (alcohol solvent) to be added were changed, while keeping the final solvent ratio without change, so as to give the final solid content of 29% by weight relative to 100 parts of the reaction solution after completion of reaction to obtain the dispersion composition (B-7′).

[0227] [Evaluation Methods]

(Weight-Average Molecular Weight (Mw))

[0228] The weight-average molecular weight was measured by GPC with the following conditions.

[0229] Instrument: HLC-8320GPC (manufactured by Tosoh Corp.)

[0230] Columns: TSK-gel G-6000 HXL, G-5000 HXL, G-4000 HXL, G-3000 HXL, and G-2000 HXL (manufactured by Tosoh Corporation)

[0231] Eluent: THF

[0232] Flow rate: 1 mL/min

[0233] Temperature: Pump oven and column oven at 40° C.

[0234] Injection volume: 100 μL

[0235] Standard substance: Polystyrene EasiCal PS-1 (manufactured by Agilent Technologies Japan Ltd.)

[0236] (Grafting Weight of Maleic Anhydride (Degree of Modification) (% by weight))

[0237] This was measured by the alkali titration method in accordance with JIS K 0070.

[0238] (Degree of Chlorination (Chlorine Content) (% by weight))

[0239] This was measured in accordance with JIS-K7229.

[0240] (Dispersibility)

[0241] This was evaluated by the viscosity of the dispersion and the appearance of the solution during preparation. The viscosity of the dispersion in a glass bottle was measured with a B-type viscometer after this bottle was immersed in a constant temperature bath at 25° C. at least for 6 hours.

A: The dispersion is uniform and milky white with the B-type viscosity of 400 mPa.Math.s or less.
B: The dispersion is uniform and milky white with the B-type viscosity of more than 400 mPa.Math.s to 700 mPa.Math.s or less.
C: The dispersion is uniform and milky white with the B-type viscosity of more than 700 mPa.Math.s to 1200 mPa.Math.s or less.
D: Precipitation occurs immediately after the dispersion is prepared, or the resin component is not dispersed in the dispersing medium, or the B-type viscosity of the obtained dispersion is more than 1200 mPa.Math.s.

[0242] (Temporal Change in Stability)

[0243] The stability of 150 g of the resin dispersion in a 250 ml glass container was evaluated visually after this was allowed to statically stand at room temperature for a predetermined period of time.

A: Excellent stability with no sedimentation even after standing for more than 3 months.
B: No sedimentation after standing for more than 3 months with some thickening, but this is still within a practical range.
C: Slight sedimentation is observed after 1 to 2 months, but this is still within a practical range.
D: Sedimentation is seen within one month and is not suitable for a practical use.

[0244] (Adhesion Test)

[0245] Linear notches were made horizontally and vertically on the coating film of the test specimen at 1 mm intervals so as to reach the substrate to create 100 compartments (square grid); then, a cellophane adhesive tape was adhered on to the square grid and pulled off to a 1800 direction. The cellophane adhesive tape was adhered and pulled off 10 times to the identical 100 compartments, and the adhesion (bonding) was evaluated based on the following criteria. When 50 or less compartments are peeled from the coating film (rating A to C), usually there is no practical problem.

A: There is no peeling of the coating film.
B: The number of the peeled compartments from the coating film is 1 or more to 10 or less.
C: The number of the peeled compartments from the coating film is more than 10 to 50 or less.
D: The number of the peeled compartments from the coating film is more than 50.

[0246] (Gasohol Resistance Test)

[0247] The test specimen was immersed in regular gasoline/ethanol=9/1 (v/v) for 120 minutes; then, the condition of the coating was observed to evaluate the gasohol resistance in accordance with the following criteria. When no peeling occurred on the surface of the coating (conditions A to C), usually there is no practical problem.

A: There is no change in the surface of the coating film.
B: Slight change is observed on the surface of the coating film, but no peeling is observed.
C: Changes are observed on the surface of the coating film, but no peeling is observed.
D: Delamination can be seen on the surface of the coating film.

[0248] The weight-average molecular weights of the modified polyolefin resins, the solvents in the dispersing medium, the total contents of the structure derived from the (meth)acrylic acid component, the solid fractions, and the evaluation results and viscosities of Examples and Comparative Examples are summarized in Table 1 below.

TABLE-US-00001 TABLE 1 Component (A): polyolefin resin Raw material Modifying component Product (Polyolefin resin) ((meth)acrylic acid component) (modified Maleic Component (C) Component (D) polyolefin Component (B): anhydride Hydroxyl Low polarity resin) dispersing medium Molecular grafting Degree of monomer monomer Molecular Aliphatic acid weight weight chlorination content content weight Alcohol hydrocarbon (Mw) (wt %) (wt %) (mol %) (mol %) (Mw) solvent solvent Example 1 60,000 2.5 15.0 5 50 80,000 IPA MCH 2 60,000 2.5 15.0 15 50 80,000 IPA MCH 3 60,000 2.5 15.0 1 50 80,000 IPA MCH 4 60,000 2.5 15.0 5 80 80,000 IPA MCH 5 60,000 2.5 15.0 5 30 80,000 IPA MCH 6 60,000 2.5 15.0 15 30 80,000 IPA MCH 7 60,000 2.5 15.0 5 50 80,000 IPA MCH 8 60,000 2.5 15.0 5 50 80,000 IPA MCH 9 60,000 2.5 15.0 5 50 80,000 IPA MCH 10 60,000 2.5 15.0 5 50 80,000 IPA MCH 11 60,000 2.5 15.0 5 50 80,000 IPA MCH 12 60,000 0 15.0 5 50 80,000 IPA MCH 13 60,000 2.5 0 5 50 80,000 IPA MCH 14 60,000 2.5 25.0 5 50 80,000 IPA MCH 15 60,000 2.5 15.0 5 50 300,000 IPA MCH 15 60,000 2.5 15.0 5 50 10,000 IPA MCH 17 110,000 2.0 17.0 4 45 120,000 BuOH MCH 18 60,000 2.5 24.5 4 45 70,000 BuOH MCH 19 110,000 2.0 17.0 4 45 120,000 PIP MCH 20 60,000 2.5 24.5 4 45 70,000 PIP MCH Comparative 1 60,000 2.5 15.0 — — — IPA MCH Example 2 60,000 2.5 15.0 0 50 80,000 IPA MCH 3 60,000 2.5 15.0 5  0 80,000 IPA MCH 4 60,000 2.5 15.0 5 50 80,000 IPA MCH 5 60,000 2.5 15.0 5 50 80,000 IPA — 6 60,000 2.5 15.0 5 50 80,000 IPA BuOAc 7 60,000 2.5 15.0 5 50 80,000 IPA MCH Dispersion composition Total contents of the structures derived from Evaluation (meth)acrylic Solid Temporal acid component fraction change in Gasohol Viscosity (wt %) (wt %) Dispersibility stability Adhesion resistance (mPa .Math. s) Example 1 60 40 A A A A 350 2 60 40 C C B C 1000 3 60 40 B C B B 600 4 60 40 A C B B 100 5 60 40 C C B B 1000 6 60 40 D C C C 1200 7  5 40 A C A A 150 8 90 40 C A C C 1000 9 20 40 A A A A 200 10 40 40 A A A A 300 11 60 30 A C C C 80 12 60 40 A B B B 350 13 60 40 A B B B 400 14 60 40 C C B B 1000 15 60 40 C C A A 1000 15 60 40 A A C C 400 17 60 40 C A A A 1000 18 60 40 B A A A 600 19 60 40 B A A A 600 20 60 40 A A A A 300 Comparative 1 — 40 D — — — — Example 2 60 40 D — — — — 3 60 40 D — — — — 4 95 40 D A D D 2000 5 60 40 D — — — — 6 60 40 D — — — — 7 60 29 A D D D 100 (Footnote to Table 1) IPA: Isopropyl alcohol PIP: Neoethanol PIP MCH: Methylcyclohexane BuOH: n-Butyl alcohol BuOAc: n-Butyl acetate

[0249] From the above results, it can be seen the following. In Comparative Example 5, where the aliphatic hydrocarbon solvent was used as the dispersing medium without the alcohol solvent, the resin component did not disperse, so that the dispersion composition could not be obtained. In Comparative Example 6, where butyl acetate was used in place of the aliphatic hydrocarbon solvent, the resin component once dispersed deposited, so that the alcohol dispersion could not be obtained. On the other hand, in each of Examples 1 to 20, where the aliphatic hydrocarbon solvent and the alcohol solvent were used as the solvent and the prescribed modified polyolefin resin was adjusted to the prescribed solid content ratio, the dispersion composition having well-balanced evaluation results could be obtained as compared to the respective Comparative Examples. From the above results, it became clear that the dispersion composition according to the present invention exhibits a moderate viscosity even with a high solid content, as well as superior stability and adhesion.